Para-alkylstyrene/isoolefin copolymers and functionalized copolymers thereof

• US 5,162,445 A
• Filed: 11/27/1989
• Issued: 11/10/1992
• Est. Priority Date: 05/27/1988
• Status: Expired due to Term

• Current Assignee: Exxon Chemical Patents Inc. (Exxon Mobil Corporation)
• Original Assignee: Exxon Chemical Patents Inc. (Exxon Mobil Corporation)
• Inventors: Chung, T-C, Dias, Anthony J., Wang, Hsien-Chang, Powers, Kenneth W., Olkusz, Joseph A.
• Primary Examiner(s): TESKIN, FRED M
• Application Number:
  US07/442,028
• Time in Patent Office: 1,079 Days
• Field of Search: 525/333.3, 525/333.4, 525/340, 525/342, 525/343, 525/350, 525/356, 525/374, 525/375, 525/379, 525/383, 525/385, 525/386, 526/347, 526/237
• US Class Current: 525/333.4
• CPC Class Codes: C08F 210/08 Butenes
• CPC Class Codes: C08F 210/10 Isobutene
• CPC Class Codes: C08F 210/14 Monomers containing five or more carbon atoms
• CPC Class Codes: C08F 212/04 containing one ring
• CPC Class Codes: C08F 212/12 Monomers containing a branched unsaturated aliphatic radical or a ring substituted by an alkyl radical
• CPC Class Codes: C08F 212/21 Bromine
• CPC Class Codes: C08F 2500/03 Narrow molecular weight distribution, i.e. Mw/Mn < 3
• CPC Class Codes: C08F 8/00 Chemical modification by after-treatment graft polymers, block polymers, crosslinking with unsaturated monomers or with polymers C08F251/00 - C08F299/00; of conjugated diene rubbers C08C
• CPC Class Codes: C08F 8/20 Halogenation
• CPC Class Codes: C08G 81/021 Block or graft polymers containing only sequences of polymers of C08C or C08F
• CPC Class Codes: C08L 23/02 not modified by chemical after-treatment
• CPC Class Codes: C08L 23/22 Copolymers of isobutene; Butyl rubber ; Homo- or copolymers of other iso-olefins
• CPC Class Codes: C08L 23/283 Halogenated homo- or copolymers of iso-olefins
• CPC Class Codes: C08L 2666/04 Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
• CPC Class Codes: C08L 2666/24 Graft or block copolymers according to groups C08L51/00, C08L53/00 or C08L55/02; Derivatives thereof
• CPC Class Codes: C08L 71/123 not modified by chemical after-treatment
• CPC Class Codes: Y02P 20/582 Recycling of unreacted starting or intermediate materials
• CPC Class Codes: Y10S 526/912 Reaction medium purification

Abstract

A copolymer of a C₄ to C₇ isoolefin and a para-alkylstyrene is provided as well as the corresponding halogenated, functionalized and grafted derivatives thereof. Processes for producing these copolymers are also provided.

Claims

1. A functionalized polymer of an isoolefin having from 4 to 7 carbon atoms and a para-alkylstyrene, wherein said functionalized polymer comprises a para-alkylstyrene moiety represented by the formula:

##STR76## wherein R and R¹ are independently selected from the group consisting of hydrogen, alkyl, primary and secondary haloalkyl; and

a functionalized para-alkylstyrene moiety having at least one type of functionalized group other than a halogen attached to said para-alkyl group, said functionalized polymer having a substantially homogeneous compositional distribution, and a ratio of Mw/Mn of less than about 6.

2. The functionalized polymer of claim 1 wherein said copolymer has a number average molecular weight of at least about 25,000.

3. The functionalized polymer of claim 1 wherein said polymer has a number average molecular weight of between about 500 and 25,000.

4. The functionalized polymer of claim 1 wherein said polymer has a ratio of M_w /M_n of less than about 2.5.

5. The functionalized polymer of claim 1 wherein said polymer has a ratio of M_w /M_n of less than about 2.

6. The functionalized polymer of claim 1 wherein said isoolefin comprises isobutylene and said para-alkylstyrene comprises para-methylstyrene.

7. The functionalized polymer of claim 1 wherein said isoolefin and said para-alkylstyrene are present in said polymer in amounts such that said isoolefin comprises from about 80 to 99.5 wt. % of said polymer and said para-alkylstyrene comprises from about 0.5 to 20 wt. % of said polymer.

8. The functionalized polymer of claim 6 wherein said polymer has a number average molecular weight of greater than about 25,000.

9. The functionalized polymer of claim 8 wherein said polymer has a ratio of M_w /M_n of less than about 2.5

10. The functionalized polymer of claim 1 wherein said isoolefin and said para-alkylstyrene are present in said polymer in amounts such that said isoolefin comprises from about 10 to 99.5 wt. % of said polymer and said para-alkylstyrene comprises from about 0.5 to 90 wt. % of said polymer.

11. The functionalized polymer of claim 10 or 7 wherein said isoolefin comprises isobutylene and said para-alkylstyrene comprises para-methylstyrene.

12. The functionalized polymer of claim 11 wherein said polymer has a number average molecular weight of greater than about 50,000.

13. The functionalized polymer of claim 12 wherein said polymer has a number average molecular weight of greater than about 100,000.

14. The functionalized polymer of claim 1 consisting essentially of the direct reaction product of isoolefin having from 4 to 7 carbon atoms and para-alkylstyrene, said polymer having a number average molecular weight of greater than about 25,000.

15. The functionalized polymer of claim 14 wherein said polymer has a ratio of M_w /M_n of less than about 2.5.

16. The functionalized polymer of claim 15 wherein said polymer has a ratio of M_w /M_n of less than about 2.0.

17. The functionalized polymer of claim 14 wherein said polymer has a number average molecular weightof greater than about 50,000.

18. The functionalized polymer of claim 17 wherein said polymer has a number average molecular weight of greater than about 100,000.

19. The functionalized polymer of claim 14 wherein said isoolefin comprises isobutylene and said para-alkylstyrene comprises para-methylstyrene.

20. The functionalized polymer of claim 14 wherein said polymer includes said para-alkylstyrene as ##STR77## wherein R and R'"'"' are independently selected from the group consisting of hydrogen, alkyl, and the primary and secondary alkyl halides, wherein y is a mixture of a halogen and at least one functional group containing oxygen, sulfur, silicon, nitrogen, carbon, and/or phosphorus.

21. The functionalized polymer of claim 20, wherein y is selected from the group consisting of alkoxide, phenoxide and carboxylates.

22. The functionalized polymer of claim 20, wherein y is selected from the group consisting of thiolates, thiophenolates, thioethers, thiocarboxylates, dithiocarboxylates, thioureas, dithiocarbamates, xanthates and thiocyanates.

23. The functionalized polymer of claim 20, wherein y is selected from the group consisting of silanes, halosilanes, malonates, cyanides, and CR'"'"'₃ wherein each R'"'"' is an organic radical.

24. The functinalized polymer of claim 20, wherein y is selected from the group consisting of amides, amines, carbazoles, phthalimides, pyridine, maleimide and cyanates.

25. The functinalized polymer of claim 20, wherein y is a phosphine.

26. The functinalized polymer of claim 20, wherein R and R'"'"' are independently selected from the group consisting of hydrogen, C₁ to C₅ alkyl and the C₁ to C₅ primary and secondary alkyl halides.

27. The functionalized polymer of claim 14, wherein said isoolefin and said para-alkylstyrene are present in said polymer in amounts such that said isoolefin comprises from about 80 to 99.5 wt. % of said polymer and said para-alkylstyrene comprises from about 0.5 to 20 wt. % of said polymer.

28. The functionalized polymer of claim 14, wherein said isoolefin and said para-alkylstyrene are present in said polymer in amounts such that said isoolefin comprises from about 10 to 99.5 wt. % of said polymer and said para-alkylstyrene comprises from about 0.5 to 90 wt. % of said polymer.

29. The functionalized polymer of claim 1 wherein the normalized differential refractive index and ultraviolet curves obtained by gel permeation chromatography for said polymer are essentially superimposable.

30. The functionalized polymer of claim 1, wherein said functionalized polymer additionally comprises a halogenated para-alkylstyrene moiety represented by the formula:

##STR78## wherein R and R¹ are independently selected from the group consisting of hydrogen, alkyl, primary and secondary haloalkyl, and where X is a halogen.

31. The functionalized polymer of claim 1 or claim 30, wherein said functionalized group is selected from the group consisting of a functional group containing oxygen, sulfur, silicon, nitrogen, carbon, phosphorus and mixtures thereof.

32. A copolymer of an isoolefin having from 4 to 7 carbon atoms and a para-alkylstyrene, said copolymer having a substantially homogeneous compositional distribution and comprising a para-alkylstyrene moiety represented by the formula:

##STR79## and a halogenated para-alkylstyrene moiety represented by the formula ##STR80## wherein R and R¹ in each of said formulas are independently selected from the group consisting of hydrogen, alkyl, primary and secondary haloalkyl, and wherein X is a halogen and wherein said copolymer has a ratio of Mw/Mn of less than about 6.

33. The copolymer of claim 32 wherein said copolymer is otherwise substantially free of any ring halogen or any halogen on the polymer backbone chain.

34. The copolymer of claim 33 wherein at least about 95 wt. % of said copolymer has a para-alkylstyrene content within about 10 wt. % of the average para-alkylstyrene content for said copolymer.

35. The copolymer of claim 34 wherein the normalized differential refractive index and ultraviolet curves obtained by gel permeation chromatography for said copolymer are essentially superimposeable.

36. The copolymer of claim 32 wherein said copolymer has a number average molecular weight of at least about 25,000.

37. The copolymer of claim 32 wherein said copolymer has a number average molecular weight of between about 500 and 25,000.

38. The copolymer of claim 32 wherein said copolymer has a ratio of M_w /M_n of less than about 2.5.

39. The copolymer of claim 32 wherein R and R'"'"' are independently selected from the group consisting of hydrogen, C₁ to C₅ primary and secondary haloalkyl.

40. The copolymer of claim 39 wherein X is selected from the group consisting of chlorine and bromine.

41. The copolymer of claim 40 wherein X comprises bromine.

42. The copolymer of claim 32, wherein said isoolefin comprises isobutylene, said R and R¹ comprise hydrogen and wherein said para-alkylstyrene moiety (1) is a para-methylstyrene moiety and wherein said halogenated para-alkylstyrene moiety (2) is a halogenated para-methylsytrene moiety.

43. The copolymer of claim 32 wherein said isoolefin and said para-alkylstyrene are present in said copolymer in amounts such that said isoolefin comprises from about 80 to 99.5 wt. % of said copolymer and said para-alkylstyrene comprises from about 0.5 to 20 wt. % of said copolymer.

44. The copolymer of claim 32 wherein said isobutylene and said para-methylstyrene are present in said copolymer in amounts such that said isobutylene comprises from about 10 to 99.5 wt. % of said copolymer and said para-methylstyrene comprises from about 0.5 to 90 wt. % of said copolymer.

45. The copolymer of claim 43 or 44 wherein said isoolefin comprises isobutylene and said para-alkylstyrene comprises para-methylstyrene.

46. The copolymer of claim 32 wherein the normalized differential refractive index and ultraviolet curves obtained by gel permeation chromatography for said copolymer are essentially superimposeable.

47. The copolymer of claim 38 wherein said copolymer has a ratio of M_w /M_n of less than about 2.

48. The copolymer of claim 32, wherein X is bromine and wherein said copolymer is otherwise substantially free of any ring bromine or any bromine on the polymer backbone chain.

49. The copolymer of claim 48 wherein R and R'"'"' are independently selected from the grop consisting of hydrogen, C₁ to C₅ alkyl, and the primary and secondary C₁ to C₅ alkyl halides.

50. The copolymer of claim 48 wherein R and R'"'"' comprise hydrogen.

51. The copolymer of claim 48 wherein the normalized differential refractive index and ultraviolet curves obtained by gel permeation chromatography for said copolymer are essentially superimposeable.

52. The copolymer of claim 48 wherein said copolymer has a number average molecular weight of greater than about 25,000.

53. The copolymer of claim 48 wherein said copolymer has a number average molecular weight of between about 500 and 25,000.

54. The copolymer of claim 48 wherein said copolymer has a ratio of M_w /M_n of less than about 2.5.

55. The copolymer of claim 48 wherein said copolymer has a ratio of M_w /M_n of less than about 2.

56. The copolymer of claim 48 wherein said copolymer has a number average molecular weight of grater than about 50,000.

57. the copolymer of claim 48 wherein said copolymer has a number average molecular weight of greater than about 100,000.

58. the copolymer of claim 48, wherein up to 60 percent of said para-alkylstyrene is present in the form of said halogenated para-alkylstyrene moiety (2).

59. The copolymer of claim 48, wherein said isoolefin comprises isobutylene.